Organic phosphite compound and method of manufacturing same



time May 6,1941 I i r 2,241,244 UNITED STAIESZPATENTYOFFICE oaamc' rnosrm'm comourm M rnon or 1mmorae'rmmrel shunt-i No Drawing. Application March 25, 1939,

Serial No. 264,119

14 Claims. (01. 260-461) This invention relates to novel organic phosbeing attached to other tom or rad alsfand phite compounds, particularly phosphite esters does not include'the unsaturated oleflns. From or alkyl ethers of alkylene glycols, and-to their ,the above, it is understood that this invention method of preparation. includes the tri-substituted normal phosphite Heretofore,.certain aryl and alkyl phosphites 5 esters, the (ii-substituted mono-hydrogen hoshave been prepared, such astriphenyl phosphite, phite esters and the mono-substituted di-hydrotricresyl phosphite,tributyl phosphite, etc. These n Ph p e t rs, In wh ch each substituent I materials have been suggestedas-additives-for' is the group form d by' Splitting Y E lubricating oil toimpart certain advantageous fronithe hy xi i rfl c l f an lkyl ether of properties thereto, particularly to inhibit bear- 1'0] a ycols leoted from the group consistin8 of ingcorrosion when employed, in, a motor oilethylene gl l, polyethylene glycols including I -diethylene glycol, triethylene glycol, etc., propy- We have now discovered that a-novel group or. 1'. lens glycol and the polypropylene glycols.

organic prosphite compoundscan be prepared in The monoallryl ethers of ethylene glycol have accordance with the method or this invehtion,*15-become familiarly known as Cellosolves; and

these compounds constituting superior additives m lkill 'of me yl 1Y v for lubricating oil having unexpected and addibecom fam a y known-as the fiCarbitols." It tional properties over those previously known. is thus understood that the p ph e sters of ded oil and the method of lubricatthe cellosolvesfiand Carbitols" are included, ing the bearings and cyiindersof internal com- 8 W as those phosnmte esters of the alkyl bustion engines with mineral lubricating oil conethers of hi h r polysly ls'iorm d by c ndenstaining these compounds are described and i s two or more ethylene oxide groups claimed in the co-pending application of Robert ethylene glycol, or formed by condensing one or E. Conary, Harry V. Ashburn and Pauls; stuts- 'm p y e e oxide groups with p o ylene h. n I The phosphite esters of alkyl ethers of alkylene A g opsg ne' 8130015 oliltaininghmore than tliree i n ention are re resented by th con ense gmups are mm, 6 Forrespm glycols of th s 1 v I p phosphite esters of the alkyl ethers thereof have x 0 such high boiling points and are so difficult of I separation that they are considered of lesser 11,0 1 I practical importance, although they are included within the scope of the present invention; In

where X1 is an alkyl-alkylene oxide group f the the case of the phosphite esters of the alkyl I ethers of the mono! or polypropylene glycols, RiiORDnflORflni is be understood that tmsmdudes I (compounds formed from propylene glycol where Rr is an alkyl radical'having less than HO CH(CI-Ia) H as well as those from the nineoarbon atoms selected from the group con- 1,3 glycol, trimethylene gly'c 01 H0 sisting oi. methyl, ethyLpropyLbutyl, amyLhexyl, CHaCHzCH: I I heptyl and octyl, where R: and Ba repres n 40 A5 representative 0! P of this the same or diflerent alkylene radicals (011K211), vention, there is mentioned" butyl .Carbito type I where n1 is zero to live, n2 is one to live, and phosphlte which 'is the trisubstituted normal in which the othertwoflpondsaresaturatediby 51'.i:orrenu'uuiimr.1alkyl,w

where X: andxsrepresent hydrogen or the same phosphite ester of the monobutyl ether or or diflerent alkyl alkylene oxide groups or the hylene glycol having the formula 25 glycol. While the polyethylene glycols and the type set iorth for X1 aboivg. :3, .tiheisetipizo orntoomomofcmomo "aikyleneradic as use 4 r t 1111' dustood that thisImclu thaIethylene radio IC4H|.0.CH:CH|-0.CH3CH$O P H H I crmocmcntoomcmo I and methyl "Cellosolve? phosphite which is the i V I 59 til-substituted normal phosphite ester of the and'the two propylene radicals I ronomethyl ether or monothylene glycol having I -theiormula I .-c.-%-c- I cmoomcrho and n H v cmomncmo-s II ,g I I cmomncmo i w n r o v'w' im n n- ,phocphorustriholida' such as trichloride, phos horus. tribromide. etc, with the other ot-thc :lycol or polyphorus trichloride and where A represents the alkylene oxide or polyalkylene oxide group 01' the corresponding glycol as shown by the following equation chloride and thereby remove the H01 'from the scene of reaction, it can be made to go to substantial completion with-the formation 01' the trichloride in the or more of an H01 sequestering reagent toform the corresponding trisubstltuted normal phosphite, an excess 01 the alcohol ether over the theoretical reacting amount apparently being beneficial from reaction and yield.

In order to produce di-substituted monohydroalkyl ethers of alkylene glycol's, the same molecular proportions of phosthe alkyl ether are used so as to replace the three chlorine atoms of the phosphorus trichloride and form the corresponding normal phosphite, but in this case two mols of the'HCl sequestering reagent are used so that one mol oi HClis lei'tto react with the normal phosphite to split off one glycol alkyl the molecule, forming the di-substituted monopresence of at least three mols ether group from whichboils below about 212 the standpoint of completeness of 1 hydrogen phosphite and the corresponding chlo- I ether, in. accordance with the equation set. forth above. These can then be j separated by distillation to recover the acid ester.

In order to form the mono-substituted dihydrogen phosphite, the corresponding ,di-substltuted monohydrogen phosphite isreacted with one mol of HCl organic solvent and in the absence of an HCl sequestering reagent, thereby producing the monosubstituted dihydrogen ester and the corresponding chloride 01' the alkyl ether; according to the equation These can then be separated by distillation.

The above reactions are carried out generally ior example as from wise to the cooled mixture, of alkyl ether, 'solve'nt and H01 sequestering reagent. After completion of. the addition of the phosphorus trichloride, the mixture is preferably r time at the boiling point of the solvent used I I ,It is then cooled, may be washed With'water to re- .55 in thepresence of a suitable.

F. In the case 01' the uxed for a period of move any free acid,

vacuum to recover the desired ester as a distillate.

Any low boiling aliphatic or aromatic hydrocarbon or chlorinated hydrocarbon solvent can be employed, although preferably one is selected F. Examples .01 hexane, heptane. and the like. If

suitable solvents are pentane, carbon tetrachloride, benzene,

dry benzene, while the temperatur v A e was maintained between 23-50 F.

After complete addiproduct passed over atabout 455-465 F. under an absolute pressure or 15-20 mm; mercury. This .Ofly colorless liquid soluble vin oil.

ing over at 290-30532; under an absolute pre's sure or 1040- mm. mercury. This material was and then dried in the prcsence of a suitable desiccant, such as anhydrous ester also an oily colorless liquid soluble in mineral lubricating oil.

Wherever theexpression phosphorus trichloride appears in the specification and claims; it is to be understood that other phosphorus trihalides are included under the doctrine of equivalents: likewise, wherever the expression HCI sequestering reagent appears in the description and claimsiit is to be understood that this includes a reagent which is active, to react with other hydrogen halides produced in the reaction by the use of phosphorus trihalides other than the chloride.

Obviously many modifications and" variations ot the invention as hereinbeiore set forth may be made without departing from the spirit and scope thereof, and only such limitations should be imposed as are indicated in the appended claims.

We claim:'

1; As a new compound, a 'phosphite ester of an allryl ether of an alkylene glycol having the formula wherexi is an alkyl-alkyleneoxide group of the ime - R1 (032) n1R3) in where R1 is an alkyl radical containing from one to eight carbon atoms, where R: and Rs repof an alkyl ether of an alkylene. glycol of the character of claim 1, which comprises reacting the corresponding alkyl ether'ot the alkylene glycol with phosphorus trihalide in the presence of an organic solventand a hydrogen halide sequestering reagent.

9. The method of preparing a normal phosphite ester or an alkyl ether oi! an alkylene glycol 0! the character of claim 1, which comprises reacting three mols or the corresponding alkyl ether of the alkylene glycol with one mol of phosphorus trlchloride in the presence of at least three mols of HCl sequestering reagent. 10. The method 01' preparing adi-substituted monohydrogen phosphite ester of an alkyl ether of an alkylene glycol or the character or claim 1, which comprises reacting three mols of the corresponding albl ether of the alkylene glycol with one mol of phosphorus trichloride in the presence or two mols or an H01 sequestering reagent.

11. The method or preparing a mono-substi tuted di-hydrogen phosphite ester of anallwl ether or an alkylene glycol of the character of claim 1, which comprises reacting one moi of the corresponding. di-substituted monohydrogen phosphite ester oi. the alkyl ether of an alkylene glycolwith one moi of'HCi with the splittin oi! of one mol of the corresponding alkyl ether resent alkylene radicals (CIHEI) selected from the group consisting of ethylene and propylene,

where n1 is zero to 5, n2 is one to five, and where X: and x: represent a chemical constituent selected from the class consisting oi. hydrogen and an alkyl-alkylene oxide'group of the type setforth for x1 'above.

2. A new compound in accordance with claim requestering reagent.

1, in which the 'alkylene glycol is an ethylene glycol having notmorethan three ethylene phoaphlte a new compound,- a phosphite ester of a,

aphosphite esterofs chlorldm 12. The method of manufac T B the normal phosphite ester'ot the mono -hutyl ether of. di-- ethylene glycol. which comprises reacting three mols of the mono-hutyl ether of -di-ethylene glycol with one mol of phosphorus trichloride' in the presence of 13. The method of phosphite the'r of ethylene glycol with .01 the mono-methyl one moi of phosphorus trlchlorlde in the presence of atleast threemols oi anHCl reot a normal a ent. 7

14. The method osphitc'esteroianalkyletherotanaikylene glycol 01 the leastthreemolsofthecorrespondingalkylether" s: an alkylene glycol; at- H61 sequestering-reagent and aims I ganic solvent, refluxingthe mixture, andthen least three mus recoverlngthereaultantphosphiteester byvac llmimdistillation.

aonmr n some means v.- mun-N.

at least three mols of an HCl:

manufacturing the normal I ester of the mono-methyl ether of ethylene glycol,'whlch reacting three mols character of claim L'which colnhailing 'or- 

